00125 - Physical Chemistry I

Learning outcomes

At the end of the course, the student possesses knowledge of termodynamics applicable to chemical systems under equilibrium conditions. They use classical thermodynamics in the study of phase equilibria in both single-component and multi-component systems, in the examination of properties of mixtures and ionic and non-ionic solutions, and in the treatment of chemical equilibrium. The student acquires the necessary skills to understand the physical principles underlying chemistry and is introduced to the applications of thermodynamics to problems in Industrial Chemistry, Analytical Chemistry, and Chemical Plants.

Course contents

Thermodynamics

• Definitions of temperature and pressure. Gas properties: ideal gases. Equations of state. Gas mixtures.

First law of Thermodynamics

• PV work. Heat. Enthalpy. Heat capacities. The Joule and Joule-Thompson experiments. State functions and line integrals. The molecular nature of the internal energy.

Second law of Thermodynamics

• Heat engines. Entropy. Calculation of entropy changes. The thermodynamic temperature scale. Material equilibrium. Entropy and equilibrium.

The Gibbs and Helmholtz functions

• Thermodynamic relations for a system in equilibrium. Calculations of changes in state functions. Chemical potential and Material equilibrium. Reaction equilibrium. Standard States. Standard enthalpy of reaction. Standard enthalpy of formation. Determinations of the standard enthalpy of formation and reaction. Temperature dependence of reaction heats. Standard Gibbs energy of reaction.Third law of Thermodynamics. Entropies and Third Law.

Reaction equilibria in ideal gas mixtures

• Chemical potential in an ideal gas mixture. Ideal-gas reaction equilibria. Temperature dependence of the equilibrium constant. Ideal-gas equilibrium calculations. Shifts in ideal-gas reaction equilibrium. One component phase equilibrium. The phase rule. The Clapeyron equation.

Real gases

• Compression factors. Real-gas equations of state. Condensation. Critical data and equations of state. The critical state. The law of corresponding state. Solutions. Solution composition. Partial molar quantities. Mixing quantities. Determination of partial molar quantities.

Ideal solutions

• Thermodynamic properties of ideal solutions. Ideally dilute solutions and their thermodynamic properties.

Non ideal solutions

• Activities, activities coefficients and their determination. Activities coefficients on the molality and molarity concentration scales. Solutions of electrolytes. Determination of electrolyte activity coefficients. The Debye-Huckel theory of electrolyte solutions. Standard-state thermodynamic properties of solution components. Non ideal gas mixtures. Reaction equilibrium in non ideal systems. The equilibrium constant. Reaction equilibrium in non electrolyte solutions, in electrolyte solutions, involving pure solids or pure liquids, in non ideal gas mixtures.Temperature and pressure dependences of the equilibrium constant.

Multi component phase equilibrium

• Colligative properties. Vapor-pressure lowering. Freezing point depression and boiling point elevation. Osmotic pressure. Two component phase diagrams. Two component liquid-vapor equilibrium. Two component liquid-liquid equilibrium.Two component liquid-solid equilibrium. Structure of phase diagrams. Solubility.

Electrochemical systems

• Electrostatics. Thermodynamics of electrochemical systems. Galvanic cells. Types of reversible electrodes. Thermodynamics of galvanic cells. Standard electrode potentials. Classification of galvanic cells. Liquid-junction potentials. Applications of EMF measurements. Batteries.

Readings/Bibliography

Each student must adopt one of the following suggested books :

-R. J. Silbey, R. A. Alberty,M. G. Bawendi, Physical Chemistry, 4th edition, Wiley, USA

- P. W. Atkins, J. De Paula, J. Keeler Chimica Fisica. Sesta edizione italiana Zanichelli, Bologna.

- A. Gambi Esercizi di Chimica Fisica, Zanichelli, Bologna.

Teaching methods

During each lecture the student will have a detailed description of the course subjects. Students will be encouraged to ask questions and stop the lecturer when in the need of further explanation. Theory demonstrations will be complemented by the lecturer solving numerical problems. Problems and exercises solved in the class will be instances of those that will be assigned for the written assessment tests.

Assessment methods

The final assessment comprises a written test and an oral examination, both on the various subjects of the course. The written test precedes the oral one and in the former the student must correctly solve five physical chemistry problems, each with a maximum mark of 6. One problem concerns the equilibrium of chemical reactions, one the phase equilibrium, one electrochemistry and two are about applications of the Thermodynamic Principles to transformation of closed system. During the test the student must use his/her pocket scientific calculator and look for physical chemistry property values in suitable literature sources. The time at disposal for the test is 4 hours, during which also personal lecture notes are made available. The written test is passed if a minimum of 18/30 marks is attained and this provide the access to the second part of the assessment, that is the oral exam. The student will be requested, during the oral exam, to answer three questions about subjects of the course. Each question has a maximum score of 10. The oral examination is passed if the student gets at least 18/30 marking. The average of the marks of the written and oral examinations will make the final score.

Teaching tools

Lecture handouts and notes will be available by username and password at https://virtuale.unibo.it/ of the University of Bologna.

Office hours

See the website of Filippo Tamassia